EP1563888B1 - Zusammensetzung zur Wasserbehandlung und Verfahren zu deren Herstellung - Google Patents

Zusammensetzung zur Wasserbehandlung und Verfahren zu deren Herstellung Download PDF

Info

Publication number
EP1563888B1
EP1563888B1 EP05103828A EP05103828A EP1563888B1 EP 1563888 B1 EP1563888 B1 EP 1563888B1 EP 05103828 A EP05103828 A EP 05103828A EP 05103828 A EP05103828 A EP 05103828A EP 1563888 B1 EP1563888 B1 EP 1563888B1
Authority
EP
European Patent Office
Prior art keywords
adhesive
water
chloride
silver chloride
water treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP05103828A
Other languages
English (en)
French (fr)
Other versions
EP1563888A2 (de
EP1563888A3 (de
Inventor
Joseph A. King
Martin Robert Edelson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
King Technology Inc
Original Assignee
King Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/550,668 external-priority patent/US6446814B1/en
Priority claimed from US09/707,114 external-priority patent/US6652871B1/en
Application filed by King Technology Inc filed Critical King Technology Inc
Publication of EP1563888A2 publication Critical patent/EP1563888A2/de
Publication of EP1563888A3 publication Critical patent/EP1563888A3/de
Application granted granted Critical
Publication of EP1563888B1 publication Critical patent/EP1563888B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/685—Devices for dosing the additives
    • C02F1/688—Devices in which the water progressively dissolves a solid compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C02F2201/006—Cartridges
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor

Definitions

  • This invention relates generally to a dual filter system and apparatus and more specifically to a replaceable water filter carrying a water purification composition dispersibly secured therein to enable the water filter to simultaneously and in situ purify water as water flows through the water filter while minimizing disruption to the normal flow of water through the filter system.
  • bacteria killing materials such as metal ions are effective in killing bacteria.
  • metal ion is the silver ion and another commonly used bacteria killing and material is the zinc ion.
  • Other types of ions are used as algaecides.
  • the difficulty in use of metal ions is to maintain the ion concentration within proper ranges since too low metal ion concentration results in ineffective killing of bacteria and to high metal ion concentrations can be harmful.
  • Another difficulty is to be able to controllable release the materials to provide for water purification over an extended period of time.
  • a bacteria killing material I use an adhesive that is securable to both a metal ion generating material and to a particle carrier that can be placed in a container within the water supply. Water can be allowed to flow through the container as the bacteria killing material controllable release metal ions to kill bacteria in the water While the use of bacteria killing materials that release metal ions is known the present invention is directed to the structure and mechanism for holding the bacteria killing materials so as not to interfere with the release of the bacteria killing materials such as metal ions without disrupting the normal flow of water through the system.
  • a filter is included that removes unwanted waste particles from the water.
  • a container is placed in the core of the filter.
  • the container is filled with a bacteria killing material such as chlorine or bromine
  • a bacteria killing material such as chlorine or bromine
  • devices placed in the core of the filter create obstructions to normal flow though the fluid filter.
  • the first obstruction to normal flow is the container itself which hold the bactericide and the second obstruction to normal flow is the materials that arc placed in the container.
  • the obstruction to normal flow of water through the filter system is substantially eliminated as the bacteria killing material is either secured directly to the filter medium or to a portion of the filter where the flow area is generally the largest thereby allow ing one to maintain the normal flow patterns of the filter mechanism.
  • a water purification material such as a bacteria killing material
  • a replaceable filter that normally removes debris from the water.
  • Such filter can perform a dual in situ function in that the filter simultaneously removes debris and kills bacteria Consequently, when the filter is replaced due to accumulation of debris thereon the bacteria killing material is replaced in the same operation thus minimizing the consumer maintenance in maintaining a water system in proper condition.
  • the present invention becomes consumer friendly as the need for maintenance of the system can be reduced.
  • EP 0 804 877 A describes D1 a water treatment composition using a substrate onto which an adhesive such as an epoxy resin is secured; within the adhesive, a antimicrobial agent such as zinc chloride or zinc sulphate is provided for slow release of metal ions upon contact with water.
  • an adhesive such as an epoxy resin
  • a antimicrobial agent such as zinc chloride or zinc sulphate
  • the present invention comprises a water treatment composition for maintaining a metal ion aqueous concentration at a bacteria controlling level comprising:
  • the present invention further comprises method of making an article for in situ water treatment comprising the steps of:
  • the water treatment composition comprises a carrier and a metal ion yielding material which is secured to a filter medium.
  • Attached to the carrier is a bacteria killing material which, in the preferred embodiment, comprises silver chloride (AgCl) coating located thereon.
  • the silver chloride particles are suspended in an adhesive matrix that adhesively secures the silver chloride particles proximate thereto in an ion yielding relationship.
  • Another suitable metal ion yielding material suitable for use is zinc.
  • the bacteria killing material is a metal ion yielding material .
  • An example of silver ion yielding material is silver chloride which is described more fully in my co-pending application Scrial Number 08/957,265, filed October 24, 1997, titled Water Treatment Composition
  • Silver chloride is a white powder that can be melted or cast like a metal, and is derived from heating a silver nitrate solution and adding hydrochloric acid or salt solution to produce a silver chloride solution which is then boiled or filtered either in the dark or under a ruby red light to produce the silver chloride powder.
  • the silver chloride while still in solution is combined with an adhesive to form an adhesive silver chloride solution.
  • the adhesive and the silver chloride solution are then applied to a carrier such as a pellet.
  • the adhesive is then cured to produce a pellet having a silver chloride coating adhesively adhered thereto with both the zinc and the silver chloride available for reacting with the chemicals within a bacteria cell to kill or damage the bacteria.
  • the silver chloride while still in solution is combined with an adhesive to form an adhesive silver chloride solution which is applied directly to a filter material for use in screening waste particles from a water source.
  • adhesively secured herein is meant to include a surface attachment structure that does not prevent the bacteria killing materials from releasing the ions to kill unwanted bacteria.
  • Adhesive matrix coating 12 comprises an adhesive that secures itself to the surface of both the silver ion generating material, which comprises silver chloride 13 and to the carrier, which is shown as a pellet 11.
  • the carrier 11 could be an active carrier, such as zine as multiple ion generating material may be suitable for killing different types of bacteria.
  • FIG 2 is a cross-sectional view of the silver chloride coated pellet 10 of Figure 1 showing carrier particle 11 centrally located within adhesive matrix 12 that contains silvcr chloride 13 dispersed throughout the adhesive matrix 12.
  • the silver chloride 13 is maintained in the water porous matrix proximate the carrier pellet 11 to enable water to contact both the silver chloride located within the matrix.
  • These typc of pellets 11 can be placed directly into a container in the water to allow the bacteria killing materials to be released into the water.
  • the pellets containing the bacteria killing materials arc secured directly to a filter medium so that the bacteria killing materials controllable release metal ions over an extended period of time.
  • a silver ion yielding material such as silver chloride
  • a suitable material for adhesively securing the silver chloride proximate the carrier is polyviny acetate.
  • the present invention includes the step of securing the carriers with the ion generating material directly to the filter material used to form a mechanical filter.
  • the ion generating materials are secured directly to the fabric or filter medium without the use of a separate carrier. In both cases one obtains a dual filter system that provides for in situ killing of bacteria and removal of debris from the water flowing through the filter system.
  • the following examples illustrate how silver chloride particles were affixed proximate to the exterior surface of a carrier such as a pellet.
  • the gelatin mixture is then strained through a screen. At this point, 5 grams of sodium chloride are mixed into the gelatin mixture.
  • the gelatin mixture is then combined with the aqueous silver nitrate mixture to convert the silver nitrate into silver chloride to thereby form an aqueous silver chloride gelatin mixture.
  • a batch of pellets having a maximum dimension of about 1/8 inch are then heated to about 140 degrees F. The pellets arc then sprayed with the heated, aqueous silver chloride gelatin mixture.
  • the silver chloride gelatin mixture is then immersed in an aqueous bath of glutaraldehyde for about 12 hours to react the gelatin with the glutaraldehyde
  • the curing produce an adhesive matrix that secured the pellets with the silver chloride that is dispersed throughout the adhesive c matrix
  • the pellets, which are covered with a coating of silver chloride are rinsed and air dried to produce pellets with a silver chloride coating affixed proximate to the pellets.
  • the above process was repeated except instead of immersing the pellets with the silver chloride gelatin mixture in an aqueous bath of formaldehyde, the pellets with the silver chloride gelatin mixture were cured in an aqueous bath of formaldehyde
  • the pellets had a maximum dimension of about 1/8 of an inch Larger or smaller pellets could be used; however, for use as a water treatment composition in a dispensing valve, it is preferred to have carrier in multiple pellets in order to present a larger surface area to the water containing the bacteria. While securing of the bacteria killing material to the pellet carrier has been described the bacteria killing material can also be secured directly to the filter medium using the same adhesive.
  • the adhesive used was gelatin as gelatin is capable of adhering to the surfaces of both the carrier and the silver chloride. That is gelatin which can be cross-linked in the presence of formaldehyde or glutaraldehyde to obtain the necessary adhesive characteristics remains non-soluble in the water and unreactive with either the carrier or the silver chloride, and thus can hold the silver chloride proximate the carrier. That is the cross-linked gelatin not only forms a surface attachment but forms a matrix to support or secure the silver chloride in proximity to the surface of the pellet.
  • the gelatin matrix is securable to the surfaces of both the silver chloride and to the pellets, one is assured that the silver ion yielding material will remain proximate each other to generate ions thereof. Also, the gelatin is desirable since the porosity of the adhesive matrix formed from gelatin allows bacteria containing water access to both the silver to enable both the silver ions to kill the bacteria in the water.
  • gelatin is described as one of the adhesives, other suitable adhesives for securing the bacteria killing material to either the carrier or directly to the filter material so that the metal ions are controllable released include polyurethane, epoxy resin polyvinyl alcohol and polyvinyl acetate.
  • reference numeral 20 identifies a dual filter apparatus of the present invention for simultaneously removing debris and killing bacteria.
  • the filter 20, which is in cartridge form, includes a first end cap 21 and a second end cap 22 with a porous pleated filter medium 23 secured therebetween for screening waste particles from the water as the water flows through the filter medium 23.
  • End cap 21 is shown with an opening 21a for ingress of fluid
  • Figure 4 shows that end cap 22 includes an opening 22a for ingress of fluid into the interior 26 within the zig-zag shaped filter medium 23.
  • Figure 5 and Figure 6 show a portion of one embodiment of a porous filter medium 30 that is arranged in a cross-hatched pattern to form a network comprised of a set of vertical fibers 31, 32 and 33 supporting a set of horizontal fibers 34, 35, 36, 37 and 38 to provide a plurality of regular openings 39 therein for screening waste particles of larger size from the water.
  • a porous filter medium 30 In normal operation of the filter medium 30, water flows though the openings 39 while the large debris particles encounter the external network of fibers and arc thus prevented from flowing through the filter medium 30. In time the filter becomes clogged with waste particles and needs to be replaced.
  • the fibers are shown as round with regular shaped openings therein: however, it should be understood that the shape of the fibers, the shape of the openings as well as the use of non-fibers are suitable for making a filter for removing water carried debris as the water flows through the filter medium.
  • FIG. 7 shows the filter medium 30 with a bacteria killing material 40 dispersibly secured to the surface of the filter medium so as to minimize obstruction to normal flow through the filter housing
  • the bacteria killing material comprises silver chloride and a pellet acting as a carrier.
  • the area of the filter medium is large compared to the flow area through the core of the filter. Consequently, sufficient bacteria killing material can be dispersibly secured to the filter medium or proximate the filter medium so that the density of bacteria killing material per unit of flow area of the filter medium is small in comparison to the density of bacteria killing material which is required if the bacteria killing material is located in the core area of the filter.
  • debris material which is larger than opening 39 is prevented from passing through the filer medium by the network of fibers while the water coming into contact with the bacteria killing material on the fibers receives the bacteria killing action. While only two layers of fibers are shown, it is apparent that multiple layers of fibers can be stacked to provide a torturous path for the water to follow thereby increasing the contact between the water and the bacteria killing material.
  • Figure 7a shows a portion of the filter medium 60 wherein the separate carrier for the bacteria killing material has been dispensed with.
  • the portion of the filter medium includes fibrous members 61, 62 and 63 that intersect with members 64, 65 and 66 to form a plurality of openings 68 therethrough.
  • the bacteria killing material is dispersibly secured directly to fibers by a thin film of non-water soluble porous adhesive 70 and 71.
  • the adhesive 70 dispersibly secures the bacteria killing materials directly to the fibers of the filter medium in a condition to allow a controlled release of ions.
  • the bacteria killing material is a controllable releasable ion yielding material selected from the group of metal ion yielding materials consisting of zine sulphate, zine carbonate, zinc chloride, copper carbonate. copper sulfate, silver chloride, stannous chloride and stannic chloride.
  • Figure 8 shows a method of making a filter medium that can simultaneously filter out debris and kill bacteria with two different bacteria killing materials.
  • the filter medium manufacturing system 50 includes a first station 51 for forming a fiber 52 having a plurality of a first bacteria killing materials such as zine particles 53 secured thereto.
  • a second station 55 includes a second fiber 56 having a second bacteria killing material such as silver chloride particles 57 secured thereto
  • the fibers are directed into a third station 58 that weaves the fibers into a porous filter medium 59 comprised of fibers with a first bacteria killing material thereon and fibers with a second bacteria killing material thereon which are located in proximity to each other to thereby provide the bacteria killing action from two different bacteria killing materials
  • the filter medium which normally is used to remove debris from the water by screening the waste particles, is also used as a carrier for the first bacteria killing materials and the second bacteria killing materials which are dispersibly secured thereon so that water passing through the filter medium not only removes debris removed but also the bacteria is killed by the bacteria killing materials located on the filter medium.
  • FIG 9 is a top view a filter cartridge 70 and Figure 10 is a sectional exploded view of filter cartridge 70 taken along lines 10-10
  • Filter cartridge 70 includes a top cap member 71 and a bottom cap member 72 with a rigid core tube 73 that connects top cap member 71 to bottom cap member 72.
  • a filter medium 75 which is arranged in an annular shape with a series of pleals that extend circumferentially around the exterior of filter cartage 70 Located between core tube 73 is an annular carrier that is impregnated with a bacteria killing material and more particularly to a bacteria killing material that controllable releases metal ions into water flowing through filer medium 75 to thereby effectively kill bacteria.
  • the embodiment shown in Figure 10 comprises a dual filter apparatus for a swimming pool, hot tub or spa with the filter medium 75 comprising a network of openings therein to enable water to flow therethrough while retaining waste particles.
  • the bacteria killing material is dispersibly secured in an annular carrier insert 77 proximate the filter medium 75
  • the bacteria killing material is releasable over time so that the flow path of water through and around annular carrier insert 77 kills bacteria therein while the filter medium 75 removes waste particles to thereby enable the dual filter apparatus to simultaneously remove waste particles and kill bacteria.
  • insert 77 could be separately replaceable
  • insert 77 could also be placed directly in the line leading to or away from the filter housing or on the inside of the filter housing and proximate the outside of the filter.
  • FIG 11 is a perspective view of a porous filter sleeve 80 that has been formed from a single piece of flexible material with the material containing a sonic weld 81 that holds the material in an annular shape
  • the single piece of material can form an external sleeve for dispersibly carrying the bacteria killing material
  • the sleeve 80 includes a porous material that lets debris and water through with a bacteria killing material dispersibly secured thereto
  • the bacteria killing material is controllable releasable as water flows through the filter steeve
  • filter sleeve 80 can be placed on the outside of a filter cartridge to provide the bacteria killing materials to water flowing through the filter cartridge
  • By placing the proper size sleeve on the cartridge a user can on an after market basis match the life of the filter medium as a screeener of waste particles to the amount of bacteria killing material necessary to kill bacteria during the useful life of the filter so that the filter can simultaneously release screen waster particles and kill bacteria to provide a dual water filter apparatus
  • FIG 12 is a pictorial exploded view of filter cartridge 70 show ing the filter core tube 73 with openings 73 therein for now of water therethrough Positioned next to core tube 73 is annular sleeve 77 that carries a bacteria killing material dispersed therein that becomes an integral part of the filter That is annular sleeve 77 sits between core tube 73 and annular filter medium 75 A set of bands 75a are located in a spaced condition around the periphery of filter medium 75 to maintain the integrity of the filter medium.
  • FIG 13 is a partial schematic view of a system for water purification wherein debris and bacteria are simultaneously removed by a replaceable cartridge.
  • the water purification system includes a container 85 for holding water to be purified.
  • An outlet 86 direct water to filter housing 88 wherein a cartridge filter 89 having a filter medium with a bacteria killing material secured thereto is located.
  • a cap 90 is placed onto top of container 88 to hold filter cartridge 89 therein.
  • the water circulates back into container 85 through conduit 87.
  • the system is suitable for water purification of swimming pools, hot tubs or spas which need to maintain the water free of debris as well as free of harmful bacteria
  • metal ions such as zinc ions, copper ions, silver ions, and tin ions are suitable for killing bacteria.
  • metal ions requires a delivery mechanism that can both yield the metal ions and maintain the metal ion aqueous concentration within acceptable levels.
  • a metal ion yielding material is meant to be understood as one or more compounds that, in the presence of water, yields the metal ions from the compound(s).
  • the metal ion yielding material comprises compounds selected from the group consisting of zinc sulfate, zinc carbonate, zinc chloride, copper chloride, copper carbonate, copper sulfate, silver chloride, stannous chloride and stannic chloride.
  • Each of the above compounds is capable of yielding metal ions.
  • zinc carbonate, zinc chloride and zinc sulfate are all capable of yielding zinc ions when placed in water.
  • copper chloride, copper carbonate, and copper sulfate all yield copper ions when placed in water.
  • Silver chloride yields silver ions when placed in water and stannous chloride and stannic chloride yield tin ions.
  • the present invention provides a water treatment composition wherein the metal ion yielding materials are retained in a condition to controllably release metal ions within acceptable ranges for water treatment.
  • triple acting adhesive In order to maintain the metal ion yielding materials in a condition to controllably release metal ions into the water, a triple acting adhesive is used
  • triple acting adhesive it is meant that the adhesive can secures itself to dissimilar materials which may be in either solid or particle form
  • the adhesive should be able to secure itself to a structure and simultaneously secure itself to the metal ion yielding material to hold the metal ion yielding material in position.
  • the triple acting adhesive needs to maintain its stability over a wide range of water temperatures.
  • the adhesive also needs to limit the amount of metal ions that can be released into the water In the preferred embodiment it has been found that four individual triple acting adhesives permit securing itself to the metal ion yielding material and to a separate structure while further maintaining a controlled release of metal ions.
  • the suitable triple acting adhesives is polyvinyl acetate.
  • the triple acting adhesive polyvinyl acetate provides the controlled release of metal ions from the metal ion yielding materials selected from the group consisting of zine sulfate, zine carbonate, zine chloride, copper chloride, copper carbonate, copper sulfate, silver chloride, stannous chloride and stannic chloride.
  • Polyvinyl acetate which is a non-toxic adhesive, has been found to secure the metal ion yielding material to a structure or to a mineral which is placed in the water and at the same time provides a controlled release of the metal ions.
  • a water insoluble adhesive to secure the ion yielding material to the structure results in a water treatment composition that, when placed in water, maintains the aqueous metal ion concentration at a suitable level for prolonged bacteria killing.
  • Polyvinyl acetate has been found particularly suitable since it is nonsoluble in water and maintains its integrity over a range of water temperatures For example, a pool may have water at temperatures as low as 70° F and a hot tub may have water at temperatures as high as 104° F.
  • Polyvinyl acetate is particularly suited for such applications since it has been found that the integrity of polyvinyl acetate is maintained over a wide range of temperatures, while at the same time polyvinyl acetate permits a controlled release of metal ions into the water.
  • the metal ion yielding material can be secured to an inactive structure or to an active structure that is placed directly in the water supply.
  • the metal ion yielding material can be affixed to an active structure such as a water filter or to reactive materials that are used to maintain the proper pH of the water supply.
  • a group of suitable materials for maintaining the pH of the water and for supporting the metal ion yielding materials are magnesium carbonate, magnesium silicate, calcium silicate, calcium oxide, silicon dioxide, and calcium carbonate (limestone) or mixtures thereof.
  • an active structure selected from the group consisting of magnesium carbonate, magnesium silicate, calcium silicate, calcium oxide, silicon dioxide and calcium carbonate or mixtures thereof provide an active structure that can support the metal ion yielding material thereon.
  • the following example illustrates how the metal ion yielding material of silver chloride coating was affixed to an active structure of limestone by use of polyvinyl acetate.
  • a batch of water treatment composition was prepared using 20 pounds of limestone particles as a structure for carrying the water treatment material and using a spray coating method wherein the triple acting adhesive polyvinyl acetate was mixed with the water treatment material before application to the structure
  • silver chloride a mixture of 200 grams of silver nitrate was mixed with 74 grams of sodium chloride in a mixture of 403 grams of water and 681 grams of latex polyvinyl acetate.
  • the mixture containing the silver chloride was sprayed on the limestone which was tumbled in a container for ten minutes to distribute the adhesive and the silver chloride over the limestone.
  • the coated limestone was allowed to dry until it was non-tacky to the touch
  • the water treatment composition was placed in a test body of water and the total silver ion concentration was measured and ranged from 30 to 40 parts per billion with the silver ion concentration being maintained at less than 100 parts per billion.
  • test was conducted to measure the dissolution rate of silver from the silver chloride coated minerals produce in example 1.
  • the test unit included a four liter glass reservoir a Peristaltic pump and a 6" by 15" cartridge containing the minerals made in accordance with the method described in example 1.
  • the cartridge containing the minerals was placed in the outlet stream of a reservoir with the outlet of the cartridge returning the water to the top of the reservoir
  • Four liters of city tap water at 75° F was added to the reservoir and pumped through the system at a flow rate of 20 milliliters per minute. Water samples were taken from the bottom of the reservoir at the outlet stream of the reservoir at time intervals of 0, 1, 4, 8, 24, 72 and 120 hours.
  • a batch of water purification composition was made in accordance with Example except an equal amount of polyurethane was used as the binder instead of polyvinyl acetate The test to determine the amount of silver present was repeated The results are as follows: Time (hours) Silver (ppb) 0 1.0 1 1.0 4 23 8 26 24 33 72 37 120 33
  • the measured concentration of silver was sufficient to kill bacteria yet not sufficiently high so as to introduce problems because of the presence of high levels of metal ions.
  • the metal ion yielding material yields silver ions, it is desirable to maintain the silver concentration between 10 and 100 ppb (parts per billion).
  • the concentration of silver in the reservoir was within the acceptable range If the metal ion yielding material yields zinc or tin ions, the acceptable aqueous concentration for metal ions generally range from 100 to 2000 parts per billion (ppb). If the metal ion yielding material yields copper ions, the acceptable copper ion concentration in the water ranges from 800 to 1000 parts per billion (ppb)
  • Figure 14 shows a method or applying water purification materials to a web using a spray coating method.
  • multiple spray heads can be used to apply the adhesive onto a web moving through a chamber The purpose of the chamber is to prevent contamination of the work area due to over spraying.
  • a hopper drops particles of the metal ion yielding material onto the adhesive.
  • the coated web is then allowed to dry and rewound for use in manufacture of an article for placing in a water system for the purposes of purifying the water therein.
  • Figure 15 shows a method of applying water purification materials to a web using a calendar roll coating method
  • two roll coaters are used to roll an adhesive onto a moving web.
  • the rolls are driven and maintained in a squeezing condition on the web in order to control the thickness of the adhesive applied to the web.
  • the lower roller is partially submerged in a trough that contains a liquid adhesive. As the lower roller rotates it transfers the adhesive onto the moving web.
  • the metal ion yielding particles are applied to the moving web from a hopper.
  • the entire web can be coated with the adhesive, or separate bands can be coated with the metal ion yielding material.
  • Figure 16 shows a method of applying water purification materials to a web using a knife-over-web method.
  • this knife-over-web method two steel knives and an adhesive feed assembly are utilized to apply adhesive onto a moving web. Excessive adhesive flows over the web edges and is recirculated. The web covered with adhesive flows under the knife to limit the thickness of the adhesive coating on the web. The metal ion yielding particles are applied to the moving web from a hopper.
  • Figure 17 shows a method of applying water purification materials to strips of material using an immersion coating method.
  • the adhesive is applied to the strips and the metal ion yielding particles are drop coated to the moving article from a hopper The strips are then adhered to the outside of another structure such as a filter cartridge.
  • Figure 18 shows a slurry coating method of applying water purification materials to a web using a die coater.
  • a pressurized chamber or die is utilized to apply a mixture of adhesive and metal ion yielding metal onto a moving web
  • the adhesive and metal ion yielding materials are simultaneously applied to the moving web.
  • Figure 19 shows another slurry coating method of applying water purification materials to a web using a calendar roll coater.
  • the adhesive and the metal ion yielding material are placed in a trough and a roller extends partially into the trough to roll the mixture directly onto a moving web.
  • Figure 20 shows a transfer coating method of applying water purification materials to a semi-finished product.
  • a preassembled article such as filter contains a transfer roll to transfer a layer of adhesive onto the article.
  • a plurality of transfer rollers can be used to limit the amount of adhesive applied to the article.
  • the metal ion yielding material is then dropped onto the adhesive.
  • Figure 21 shows a die coating method of applying water purification materials to a web.
  • the die coating is applied to a continuous web, and the metal ion yielding material is drop coated on the web.
  • the water treatment material is applied to the structure by either applying the adhesive to the structure and then applying the metal ion yielding material to the structure or mixing the adhesive with the metal ion yielding material and then simultaneously applying the mixture of adhesive and metal ion yielding material to the structure.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Inorganic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Filtering Materials (AREA)
  • Laminated Bodies (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (5)

  1. Eine Zusammensetzung zur Wasserbehandlung zur Aufrechterhaltung einer wässerigen Metallionen-Konzentration mit einem Bakterien kontrollierenden Niveau, die Folgendes umfasst:
    ein Metallionen abgebendes Material, gewählt aus der Gruppe bestehend aus Zinksulfat, Zinkcarbonat, Zinkchlorid, Kupferchlorid, Kupfercarbonat, Kupfersulfat, Silberchlorid, Zinn(II)-chlorid und Zinn(IV)-chlorid;
    eine Struktur; und
    einen dreifach wirkenden Klebstoff, wobei der dreifach wirkende Klebstoff an mindestens einem der Metallionen abgebenden Materialien befestigt ist und der dreifach wirkende Klebstoff weiter an der Struktur befestigt ist, so dass, wenn die Struktur in ein Volumen von Wasser platziert wird, der Klebstoff das Metallionen abgebende Material in einem Zustand hält, in dem der Klebstoff an der Struktur und an dem Metallionen abgebenden Material befestigt bleibt, wobei die Metallionen in Wasser bei einer Konzentration gehalten werden, die ausreicht, um Bakterien darin zu töten,
    wobei der dreifach wirkende Klebstoff Polyvinylacetat ist.
  2. Die Zusammensetzung zur Wasserbehandlung gemäß Anspruch 1, worin die Struktur aktiv ist und Materialpartikel umfasst.
  3. Die Zusammensetzung zur Wasserbehandlung gemäß Anspruch 1, worin die Struktur eine aktive Struktur ist, gewählt aus der Gruppe bestehend aus Magnesiumcarbonat, Magnesiumsilikat, Kalziumsilikat, Kalziumoxid, Siliziumdioxid und Kalziumcarbonat (Kalkstein) oder Mischungen davon.
  4. Die Zusammensetzung zur Wasserbehandlung gemäß Anspruch 1, worin die Struktur ein Materialstreifen ist, wobei der Materialstreifen an einer Filterpatrone befestigt ist.
  5. Ein Verfahren zur Herstellung eines Gegenstands für die Wasserbehandlung vor Ort, das folgende Schritte umfasst:
    Auswahl eines Materials zur Wasserbehandlung aus der Gruppe bestehend aus Zinksulfat, Zinkcarbonat, Zinkchlorid, Kupferchlorid, Kupfercarbonat, Kupfersulfat, Silberchlorid, Zinn(II)-chlorid und Zinn(IV)-chlorid;
    Auswahl eines Klebstoffs, der Polyvinylacetat ist;
    Auswahl einer wasserunlöslichen festen Struktur;
    Auftragen des Klebstoffs auf die wasserunlösliche feste Struktur, um mindestens eine partielle Beschichtung darauf zu bilden;
    Auftragen des Materials zur Wasserbehandlung auf den Klebstoff auf der festen Struktur;
    Härtenlassen des Klebstoffs, um so das Material zur Wasserbehandlung sicher an der festen Struktur zu befestigen; und
    Formen der Struktur zu einem Gegenstand zur Platzierung in ein Volumen von Wasser, um es so der Struktur zu ermöglichen, das Material zur Wasserbehandlung klebend darauf zu tragen, in einem Zustand, der eine Wasserkonzentration von Metallionen von weniger als 1000 Teilen je Milliarde Teile (ppb) aufrechterhält,
    wobei das Verfahren, wenn das Material zur Wasserbehandlung Silberchlorid ist, folgende Schritte einschließt:
    a) Mischen einer ersten Menge von Silbernitrat mit einer ersten Charge von Wasser, um eine Silbernitratmischung zu bilden;
    b) Mischen einer ersten Menge von Natriumchlorid mit der Silbernitratmischung, um eine Silberchloridmischung zu bilden;
    c) Mischen eines Klebstoffs, der sowohl an Silberchlorid als auch an tragenden Partikeln befestigt werden kann und der Polyvinylacetat ist, mit einer zweiten Charge von Wasser, um eine Klebstoffmischung zu bilden;
    d) Kombination der Silberchloridmischung und der Klebstofmischung, um eine Klebstoff-Silberchlorid-Mischung zu bilden;
    e) Auftragen der Klebstoff-Silberchlorid-Mischung auf tragende Partikel; und
    f) Härten der Klebstoff-Silberchlorid-Mischung an Ort und Stelle auf den tragenden Partikeln, um tragende Partikel zu bilden, die eine Beschichtung haben, welche Silberchlorid enthält.
EP05103828A 2000-01-21 2001-01-16 Zusammensetzung zur Wasserbehandlung und Verfahren zu deren Herstellung Expired - Lifetime EP1563888B1 (de)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US707114 1991-05-23
US17755800P 2000-01-21 2000-01-21
US177558P 2000-01-21
US550668 2000-04-17
US09/550,668 US6446814B1 (en) 1999-04-22 2000-04-17 Method of making a dual filter
US09/707,114 US6652871B1 (en) 2000-01-21 2000-11-06 Delivery system and method of making article
EP01100162A EP1134012A1 (de) 2000-01-21 2001-01-16 Filter zur Behandlung von Wasser

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP01100162A Division EP1134012A1 (de) 2000-01-21 2001-01-16 Filter zur Behandlung von Wasser
EP01100162.5 Division 2001-01-16

Publications (3)

Publication Number Publication Date
EP1563888A2 EP1563888A2 (de) 2005-08-17
EP1563888A3 EP1563888A3 (de) 2005-11-23
EP1563888B1 true EP1563888B1 (de) 2012-01-11

Family

ID=27390834

Family Applications (2)

Application Number Title Priority Date Filing Date
EP01100162A Ceased EP1134012A1 (de) 2000-01-21 2001-01-16 Filter zur Behandlung von Wasser
EP05103828A Expired - Lifetime EP1563888B1 (de) 2000-01-21 2001-01-16 Zusammensetzung zur Wasserbehandlung und Verfahren zu deren Herstellung

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP01100162A Ceased EP1134012A1 (de) 2000-01-21 2001-01-16 Filter zur Behandlung von Wasser

Country Status (4)

Country Link
EP (2) EP1134012A1 (de)
AT (1) ATE540742T1 (de)
AU (1) AU778539B2 (de)
CA (1) CA2331084C (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0415869D0 (en) * 2004-07-15 2004-08-18 Burton Michael J Grey water filtering system
DE202004015240U1 (de) * 2004-09-27 2004-12-09 Silvertex Gmbh Fadensystem zur Installation in Trinkwassersystemen
US9802844B2 (en) 2012-11-08 2017-10-31 Silver Aqua, Inc. Portable pathogen deactivation method and apparatus
WO2015065808A1 (en) * 2013-10-29 2015-05-07 Silver Aqua, Inc. Portable pathogen deactivation method and apparatus
US11076716B2 (en) 2015-12-04 2021-08-03 Koninklijke Philips N.V. Filter assembly for use in a fluid container of a domestic appliance
EP3454660B1 (de) * 2016-05-12 2022-04-06 Applied Silver Inc. Artikel und verfahren zur abgabe von metallionen in wäschesysteme
CN110113946A (zh) 2016-10-31 2019-08-09 应用银股份有限公司 向分批式洗衣机和烘干机中分配金属离子
CN115479579B (zh) * 2022-10-10 2023-03-31 广州三海海洋工程勘察设计有限公司 一种海上石油平台水位计标高测量系统

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071636A (en) * 1972-11-09 1978-01-31 Matsushita Electric Industrial Co., Ltd. Method of producing sheet-formed bactericidal article
FR2206278B1 (de) * 1972-11-09 1976-10-01 Matsushita Electric Ind Co Ltd
IL51212A (en) * 1976-01-14 1980-03-31 Pall Corp Filter elements and process for their continuous production by laydown of thermoplastic fibers on a preformed core to form a nonwoven cylindrical web
US4780197A (en) 1986-05-07 1988-10-25 Rainbow Lifegard Products, Inc. Chlorination module for cartridge filter unit
DE3624414A1 (de) * 1986-07-18 1988-01-28 Michael Busch Wasserfilter
DE3719233A1 (de) * 1987-06-09 1988-12-22 Erich Busch Selbsttragender filterkoerper
US5185415A (en) * 1989-07-12 1993-02-09 Japane Vilene Co., Ltd. Adsorptive resin for microorganisms
US5338340A (en) * 1990-02-10 1994-08-16 D-Mark, Inc. Filter and method of making same
CA2201934C (en) * 1994-10-05 2008-03-18 Makoto Hayakawa Antimicrobial solid material, process for producing the same, and method of utilizing the same
US6217892B1 (en) * 1997-10-24 2001-04-17 Joseph A. King Water treatment composition

Also Published As

Publication number Publication date
EP1563888A2 (de) 2005-08-17
CA2331084A1 (en) 2001-07-21
CA2331084C (en) 2011-10-25
EP1563888A3 (de) 2005-11-23
AU1637001A (en) 2001-07-26
AU778539B2 (en) 2004-12-09
EP1134012A1 (de) 2001-09-19
ATE540742T1 (de) 2012-01-15

Similar Documents

Publication Publication Date Title
US6446814B1 (en) Method of making a dual filter
US7594520B2 (en) Method of making a dual filter
US6190547B1 (en) Water treatment system
US6592766B2 (en) Water treatment dispensers
EP1563888B1 (de) Zusammensetzung zur Wasserbehandlung und Verfahren zu deren Herstellung
US3872013A (en) Bactericidal water purifier for dechlorinated water
US6383507B1 (en) Water treatment composition
US20110094972A1 (en) Water treatment
AU3057397A (en) Pour-through and pitcher mounted water filter
US20110027487A1 (en) Delivery system and method of making article
JP2004113852A (ja) 酸素供給水冷却装置及び濾過装置並びにこれ等を用いた濾過機能付随水冷却装置
AU2004218688B2 (en) Water Treatment
KR20060133545A (ko) 은 담지 입자 및 그 제조방법
US20090304868A1 (en) Controlled release cooling additive composition
JP3720079B2 (ja) 水処理剤及びその製造方法
JP3140099U (ja) 濾過装置
JPH08299855A (ja) シャワーヘッド
JP3686865B2 (ja) 酸化チタン光触媒使用による濾過器と送水管とかならる送水装置
JPH1176377A (ja) 抗菌装置
MXPA98009076A (en) Water filter on mounted and vert line
JPH04210292A (ja) 殺菌濾過装置及びそれに使用する殺菌濾床の製造方法
JPH04191854A (ja) 感光材料処理装置
CS240183B1 (en) Method of drinking-water final treatment and agent for its performance

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AC Divisional application: reference to earlier application

Ref document number: 1134012

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

17P Request for examination filed

Effective date: 20060310

AKX Designation fees paid

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

17Q First examination report despatched

Effective date: 20070307

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AC Divisional application: reference to earlier application

Ref document number: 1134012

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 540742

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60145962

Country of ref document: DE

Effective date: 20120315

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120511

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120412

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 540742

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120801

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60145962

Country of ref document: DE

Effective date: 20120801

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

26N No opposition filed

Effective date: 20121012

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120411

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120422

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120116

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20140131

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150202